Unifying the 2e– and 4e– Reduction of Oxygen on Metal Surfaces

Venkatasubramanian Viswanathan; Heine Anton Hansen; Jan Rossmeisl; Jens K. Nørskov

doi:10.1021/jz301476w

Unifying the 2e^–and 4e^– Reduction of Oxygen on Metal Surfaces

Venkatasubramanian Viswanathan, Heine Anton Hansen, Jan Rossmeisl, Jens K. Nørskov

Stanford University

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Abstract

Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e^–versus 4e^– reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔG_OH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e^– and 4e^– reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e^– reduction, this weak binding is optimal for the 2e^– reduction to H₂O₂. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.

Original language	English
Journal	The Journal of Physical Chemistry Letters
Volume	3
Issue number	20
Pages (from-to)	2948-2951
ISSN	1948-7185
DOIs	https://doi.org/10.1021/jz301476w
Publication status	Published - 2012

Bibliographical note

© 2012 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Keywords

selectivity
activity volcano
electrocatalysis
fuel cells
hydrogen peroxide
lithium-air batteries

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